JP6079334B2 - Optical semiconductor light emitting device, lighting apparatus, display device, and color rendering control method - Google Patents

Description

  The present invention relates to an optical semiconductor light emitting device, a lighting fixture including the same, a display device, and a color rendering control method.

White light semiconductor light emitting device includes a combination of a blue light semiconductor element and a yellow phosphor, a combination of a near ultraviolet light semiconductor light emitting element and a red phosphor, a green phosphor, a blue phosphor, a red light semiconductor light emitting element And a combination of a green light semiconductor and a blue light semiconductor light emitting element.
In these optical semiconductor light-emitting devices, a sealing material having a high refractive index may be used for the purpose of increasing the luminance, and there is a method of adding metal oxide particles to the sealing material when increasing the refractive index of the sealing material. is there.
Red light semiconductor light emitting device (AlGaInP system, refractive index 3.2, emission wavelength 630 nm) and green light semiconductor light emitting device (InGaN system, refractive index 2.4, light emission wavelength 530 nm) and blue light semiconductor light emitting device (InGaN system, refractive index 2) .4, in a white light semiconductor light emitting device that combines a light emission wavelength of 450 nm), since the refractive index of the light semiconductor light emitting element differs depending on the light emission color (wavelength), The difference in refractive index is different. In addition, when the refractive index of the encapsulant is wavelength-dependent, even if the refractive index of the optical semiconductor light-emitting element does not change depending on the emission color (wavelength), the optical semiconductor light-emitting element and the encapsulant are changed depending on the emission color. The refractive index difference is different.

An optical semiconductor light-emitting device in which two or more optical semiconductor light-emitting elements having different emission wavelengths are mounted, and the refractive index of the encapsulant is wavelength-dependent, and when the refractive index increases as the wavelength decreases, the optical semiconductor with a short emission wavelength Since the difference between the refractive index of the light-emitting element and the refractive index of the sealing material is small (the refractive index of the sealing material is high, the refractive index of the optical semiconductor element is approached). The amount of light extracted from the element to the sealing material increases. This effect becomes more prominent when fine particles having a high refractive index but a small Abbe number are dispersed in the encapsulant for the purpose of increasing the luminance of the optical semiconductor light emitting device.
In an optical semiconductor light-emitting device having two or more optical semiconductor light-emitting elements having different emission wavelengths, if the wavelength dependency of the refractive index of the encapsulant is large, the emission color component amount on the short wavelength side is the emission color component on the long wavelength side. There is a problem that the color rendering property is lowered by the relative increase of the amount and the balance of the luminescent color components being changed. In addition, when the emission color on the short wavelength side is blue, as in a white light semiconductor light-emitting device equipped with three primary color light-emitting semiconductor light-emitting elements, the amount of blue component in white light increases, and the human body Long-term exposure causes problems such as blue light retinopathy of the eye, physiological damage and arousal level to the skin, autonomic nervous function, body clock, melatonin secretion and the like.

As a method for improving color rendering, for example,
Warm white LED that emits white light with strong yellow color tone, cool white LED that emits white light with strong blue color tone, and red, green, and blue light for optimal “white” dimming A method including three primary color LEDs (Patent Document 1),
An optical color filter that reflects or absorbs short wavelength light is arranged between the LED elements in the visible light LED device in which the LED elements are stacked, and prevents light having a shorter wavelength from entering the longer wavelength LED element; and A method of emitting light of a desired color at a desired intensity (Patent Document 2),
A white LED (Patent Document 3) that has a high refractive index and a high efficiency of taking out light into the gas by using a fluorine-containing resin having a large Abbe number and a small chromatic aberration.
A method for suppressing a change in the Abbe number by changing the amount of a component of a compound such as monoallyl diglycidyl isocyanurate or monoallyl isocyanurate (Patent Document 4),
A method of maintaining the transparency of the transparent composite resin by setting the Abbe number after curing of the transparent resin to 45 or more and matching the wavelength dependence of the refractive index of the glass filler and the transparent resin as much as possible (Patent Document 5),
Etc. have been proposed.
Further, when a cured silicone resin is used as a lens molding material, the Abbe number is preferably 40 or more and 90 or less, and if it is smaller than 40, chromatic aberration is increased (Patent Document 6).

JP 2009-211819 A JP 2008-263127 A Japanese Patent No. 5020480 JP 2011-105784 A Japanese Patent Laid-Open No. 2005-029668 JP 2012-007002 A

In Patent Document 1, the color rendering properties of individual optical semiconductor light emitting devices are not aimed, but the color rendering properties are improved as an assembly of optical semiconductor light emitting devices. In general use, there is an economic problem.
In Patent Document 2, color rendering is improved as an optical semiconductor light emitting element. However, in an optical semiconductor light emitting device, the cost of the optical semiconductor light emitting element is the highest, which further increases the cost of the optical semiconductor light emitting element. It is a problem.
In Patent Documents 3, 4, and 6, the chromatic aberration of the optical semiconductor light-emitting device is reduced by increasing the Abbe number of the sealing material. This is a reduction in chromatic aberration of light emitted from the sealing material to the outside air, that is, The purpose is to reduce color separation, and it does not improve the color rendering by controlling the amount of light extracted from the optical semiconductor light emitting elements having different emission wavelengths. Furthermore, in patent document 3, there exists a problem also economically from using a high-cost fluorine-containing resin. In Patent Document 4, an isocyanurate-based material that suppresses a change in the Abbe number causes heat coloring. In Patent Document 6, the refractive index and the Abbe number of the silicone resin composition are limited by the functional group structure in the silicone resin.
Patent Document 5 aims to approximate the Abbe number in order to achieve a transparent composite of a glass filler and a resin, and also controls the amount of light extracted from an optical semiconductor light emitting element having a different emission wavelength. It does not improve color rendering.

  In light of the above, an object of the present invention is to provide an optical semiconductor light emitting device having high luminance and excellent color rendering, a lighting apparatus and a display device including the optical semiconductor light emitting device, and a color rendering control method. It is.

As a result of diligent investigations, the present inventors have cured two or more photosemiconductor light-emitting elements having different emission wavelengths provided in the photosemiconductor light-emitting device with a sealing composition containing specific fine particles. It discovered that the said subject was solved by sealing with the optical-semiconductor sealing material whose Abbe number is 30 or more, and completed this invention.
That is, the present invention is as follows.

[1] An optical semiconductor light emitting device including two or more optical semiconductor light emitting elements having different emission wavelengths,
The optical semiconductor light-emitting element is sealed by an optical semiconductor sealing material having an Abbe number of 30 or more obtained by curing a sealing composition containing fine particles.
The fine particles are surface-modified with a surface modifying material having one or more functional groups selected from alkenyl groups, H-Si groups, and alkoxy groups, and are made of a material that does not absorb light in the optical semiconductor emission wavelength region. An optical semiconductor light emitting device which is fine particles having an average primary particle size of 3 nm or more and 20 nm or less.
[2] The optical semiconductor light emitting device according to [1], wherein the Abbe number of the fine particles is 30 or more.
[3] The optical semiconductor light-emitting device according to [1] or [2], wherein the optical semiconductor sealing material has a transmittance from a wavelength of 400 nm to a wavelength of 800 nm of 70% or more.
[4] The optical semiconductor according to any one of [1] to [3], wherein the color rendering property is controlled by adjusting the refractive index and Abbe number of the optical semiconductor sealing material by changing the content of the fine particles. Color rendering property control method of light emitting device.
[5] An optical semiconductor light emitting device whose color rendering is controlled by the color rendering control method according to [4].
[6] A lighting fixture comprising the optical semiconductor light-emitting device according to any one of [1] to [3] and [5].
[7] A display device comprising the optical semiconductor light-emitting device according to any one of [1] to [3] and [5].

According to the present invention, the balance between the amount of light extracted from the light emitting element on the short wavelength side and the amount of light extracted from the light emitting element on the long wavelength side can be adjusted, and the color rendering can be improved. An optical semiconductor light-emitting device having excellent color rendering properties, a lighting fixture and a display device including the optical semiconductor light-emitting device can be provided.
Further, according to the present invention, since the color rendering property can be controlled by adjusting the refractive index and Abbe number of the optical semiconductor sealing material by changing the content of fine particles, a method for controlling the color rendering property of the optical semiconductor light emitting device is provided. be able to.

It is a schematic sectional drawing which shows an example of the optical semiconductor light-emitting device of this invention. It is a schematic sectional drawing which shows another example of the optical semiconductor light-emitting device of this invention. It is a schematic sectional drawing which shows another example of the optical semiconductor light-emitting device of this invention. It is a schematic sectional drawing which shows another example of the optical semiconductor light-emitting device of this invention. It is a schematic sectional drawing which shows another example of the optical semiconductor light-emitting device of this invention.

[Optical semiconductor light emitting device]
The optical semiconductor light-emitting device of the present invention is an optical semiconductor light-emitting device including two or more optical semiconductor light-emitting elements having different emission wavelengths, and has an Abbe number of 30 or more obtained by curing a sealing composition containing fine particles. The optical semiconductor light-emitting element is sealed with an optical semiconductor sealing material, and the fine particles are surface-modified with a surface modification material having one or more functional groups selected from alkenyl groups, H-Si groups, and alkoxy groups. These are fine particles having an average primary particle diameter of 3 nm or more and 20 nm or less made of a material that does not absorb light in the optical semiconductor emission wavelength region.

(Optical semiconductor light emitting device, etc.)
As an optical semiconductor light emitting device including optical semiconductor light emitting elements having different emission wavelengths in the same optical semiconductor light emitting device, for example, a red optical semiconductor light emitting element having an emission wavelength of about 630 nm and an emission wavelength of about 530 nm A white light semiconductor light-emitting device including a three-primary-color light-emitting element of a green light semiconductor light-emitting element and a blue light semiconductor light-emitting element having an emission wavelength near 450 nm.
In the case of a white light semiconductor light emitting device in which two or more optical semiconductor light emitting elements having different emission wavelengths are provided in the optical semiconductor light emitting device, the number of optical semiconductor light emitting elements for bringing the light of the optical semiconductor light emitting device closer to a desired color There are no particular restrictions on the type.

Further, in order to synthesize and approximate the light of the optical semiconductor light emitting device to a desired color, two or more optical semiconductor light emitting elements having different emission wavelengths and a phosphor that converts the emission wavelength may be combined. As said fluorescent substance, well-known fluorescent substances, such as a yellow fluorescent substance, a green fluorescent substance, and a red fluorescent substance, can be used, for example.
Further, the shape of the optical semiconductor sealing material may be a flat shape or a lens shape such as a convex shape and a concave shape, and a resin single layer (contained only of resin and containing fine particles) on the optical semiconductor sealing material. May be provided.

(Example of an optical semiconductor light emitting device)
An embodiment of the optical semiconductor light emitting device of the present invention will be described with reference to FIGS.
As shown in FIG. 1, the embodiment of the optical semiconductor light emitting device of the present invention has two or more optical semiconductor light emitting elements 10 having different emission wavelengths arranged in the concave portion of the substrate, and contains a sealing composition containing fine particles so as to cover it. The optical semiconductor sealing material layer 12 which hardened | cured was provided. The surface shape of the air interface phase 13 is not particularly limited, and may be a flat shape (convex lens shape) or a concave shape as shown in FIG. 2 in addition to a flat shape as shown in FIG.

  Further, as shown in FIG. 3, a single resin layer (a layer made of only resin and containing no fine particles) 14 may be provided on the optical semiconductor sealing material layer 12. The single resin layer 14 in FIG. 3 is convex, but it may be flat or concave. Further, in the case where the optical semiconductor light emitting device of the present invention includes a phosphor, the optical semiconductor light emitting element 10 is disposed as shown in FIG. 4, and the phosphor 11 covers the optical semiconductor sealing material layer 12 so as to cover it. As shown in FIG. 5, the phosphor 11 may be provided in a resin single layer 14 provided on the optical semiconductor sealing material layer 12.

(Optical semiconductor encapsulant)
The optical semiconductor encapsulant (hereinafter sometimes simply referred to as “encapsulant”) is for encapsulating the above optical semiconductor light-emitting element, and is obtained by curing a sealing composition containing fine particles described later. It is done.
The Abbe number of the optical semiconductor encapsulant is 30 or more, and preferably 35 or more, more preferably 40 or more from the viewpoint of further improving the color rendering. Further, the Abbe number of the optical semiconductor sealing material is usually 60 or less, preferably 55 or less. If the Abbe number is less than 30, the spread of the difference between the refractive index of the optical semiconductor light-emitting element having a short emission wavelength and the refractive index of the sealing material cannot be suppressed due to the wavelength dependence of the refractive index of the sealing material. The light extraction amount of the light semiconductor light emitting element on the short wavelength side with respect to the light extraction amount of the light semiconductor light emitting element on the long wavelength side is remarkably increased, and the color rendering is deteriorated. On the other hand, it is possible to increase the Abbe number by selecting Al ₂ O ₃ as fine particles having a large Abbe number and dimethyl silicone as a resin having a large Abbe number, and combining them. If it exceeds V, the content of Al ₂ O ₃ particles in the sealing material increases, so that the viscosity of the sealing material may be remarkably increased, and the sealing workability may be lowered. Moreover, since there is much particle | grain content, the transparency of a sealing material falls and a brightness | luminance may fall.
The Abbe number (ν _d ) is calculated from the refractive indices of the Fraunhofer line d line (587 nm), F line (486 nm), and C line (656 nm), ν _d = (n _d −1) / (n _F −n). _C ).

  In addition, the optical semiconductor encapsulant preferably has a transmittance of 70% or more and 75% or more when measured with an integrating sphere having a wavelength of 400 nm to a wavelength of 800 nm in a state where the phosphor is not included. More preferably, it is more preferably 80% or more. When the transmittance is 70% or more, light scattering caused by fine particles and light absorption by the resin itself can be suppressed, and a decrease in luminance of the optical semiconductor light emitting device can be suppressed. In order to obtain the transmittance as described above, the particle size and amount of the fine particles may be adjusted, or the resin itself may be selected.

The fine particles contained in the sealing composition are made of a material that does not absorb light in the optical semiconductor emission wavelength region. Here, the fact that there is no light absorption does not mean that there is no light absorption, but means that it is not necessary to consider the absorption substantially.
The Abbe number of the fine particles is preferably 30 or more, more preferably 35 or more. If the Abbe number of the fine particles is 30 or more, even if it is combined with diphenyl silicone having a small Abbe number or a high refractive index resin into which a halogen element is introduced, it is possible to suppress a decrease in Abbe number as an optical semiconductor encapsulant. it can.

Examples of the fine particles include inorganic particles, organic resin particles, and fine particles obtained by dispersing and compounding inorganic particles in organic resin particles.
In consideration of the monodispersibility in the resin contained in the sealing composition and the ease of surface modification to ensure the interface affinity with the resin, inorganic particles are preferable, and among the inorganic particles, metal oxidation is preferable. things more preferably, without further coloring the sealing material, SiO ₂ Abbe number is 30 or _{more, Al 2 O 3, ZrO 2} , CeO 2, Y 2 O 3, La 2 O 3, Hf 2 O 3 Is more preferable. In particular, SiO ₂ , Al ₂ O ₃ , and ZrO ₂ having an Abbe number of 35 or more and capable of obtaining nanometer-sized particle diameters from the viewpoint of maintaining the transparency of the sealing material are preferable.

The average primary particle size of the fine particles is 3 nm or more and 20 nm or less, preferably 4 nm or more and 15 nm or less, and more preferably 5 nm or more and 10 nm or less.
If the average primary particle size is less than 3 nm, the relative specific surface area of the fine particles is large, so that there are more surface modifying materials that modify the surface of the fine particles in order to ensure monodispersity in the resin and interface affinity with the resin. The cured product of the sealing material composition becomes brittle due to an increase in the reactive crosslinking points between the modifying material and the resin, and cracks occur when an environmental temperature difference occurs. Further, since the amount of the fine particle component in the surface-modified fine particles is reduced, the Abbe number control effect of the sealing material by the fine particles is lowered. In particular, when a metal oxide is selected as the fine particles, the crystallinity of the metal oxide particles is lowered, and the effect of controlling the Abbe number of the sealing material by the fine particles is reduced.
On the other hand, when the average primary particle size exceeds 20 nm, scattering by the fine particles increases, and the translucency of the sealing material is lowered, and the luminance of the optical semiconductor light emitting device is lowered.

  The content of the fine particles in the sealing composition is preferably 20 to 70% by mass, and more preferably 25 to 60% by mass. Further, in order to enable the injection workability of the sealing composition, the viscosity of the sealing composition is preferably set to 100 Pa · s or less (room temperature). It is more preferable that it is 25-50 mass% from a viewpoint which can adjust.

The fine particles contained in the sealing composition are surface modified with a surface modifying material having one or more functional groups selected from alkenyl groups, H-Si groups, and alkoxy groups.
In order to disperse the fine particles in the sealing material, it is necessary to ensure the interface affinity between the fine particle surface and the resin used for the sealing composition. The structure of the surface modification material having one or more functional groups selected from alkenyl groups, H-Si groups, and alkoxy groups has the above functional groups because it is compatible with the resin used in the sealing composition. By coating the surface of the fine particles with the surface modifying material, the interface affinity between the fine particle surface and the resin is ensured, and the fine particles can be uniformly dispersed in the sealing material.
In addition, in order to further enhance the surface affinity between the fine particle surface and the resin, or to modify the surface modifying material having the functional group more efficiently in the process of modifying the surface of the fine particle, the surface having the functional group. A known surface modifying material other than the modifying material can be used in combination.

  The alkenyl group crosslinks with the H-Si group in the resin, the H-Si group crosslinks with the alkenyl group in the resin, and the alkoxy group condenses with the alkoxy group in the resin or the alkoxy group of the surface modification material through hydrolysis. Therefore, the fine particles are not phase-separated in the process of curing the sealing composition, and can be fixed in the sealing material while maintaining a dispersed state, and the denseness of these layers can be improved.

  Examples of the surface modifying material having one or more functional groups selected from alkenyl groups, H-Si groups, and alkoxy groups include vinyltrimethoxysilane, alkoxy one-end vinyl one-end dimethyl silicone, alkoxy one-end vinyl one-end methyl. Phenyl silicone, alkoxy one-end vinyl one-end phenyl silicone, methacryloxypropyltrimethoxysilane, acryloxypropyltrimethoxysilane, methacrylic acid and other carbon-carbon unsaturated bond-containing fatty acids, dimethylhydrogensilicone, methylphenylhydrogensilicone, phenyl Hydrogen silicone, dimethylchlorosilane, methyldichlorosilane, diethylchlorosilane, ethyldichlorosilane, methylphenylchlorosilane, diphenylchlorosilane, phenyldichloro Silane, trimethoxysilane, dimethoxysilane, monomethoxysilane, triethoxysilane, diethoxymonomethylsilane, monoethoxydimethylsilane, methylphenyldimethoxysilane, diphenylmonomethoxysilane, methylphenyldiethoxysilane, diphenylmonoethoxysilane, alkoxy Examples include terminal phenyl silicone, alkoxy both-end methyl phenyl silicone, alkoxy group-containing dimethyl silicone resin, alkoxy group-containing phenyl silicone resin, alkoxy group-containing methyl phenyl silicone resin, and the like.

The surface modification amount of the surface modification material having one or more functional groups selected from alkenyl groups, H-Si groups, and alkoxy groups is preferably 1% by mass or more and 80% by mass or less with respect to the mass of the fine particles. . When the content is 1% by mass or more, the number of bonding points with the functional group contained in the resin increases, and phase separation of the fine particles hardly occurs during the process of curing the sealing material. Scattering can be prevented and transparency can be maintained. Moreover, it can prevent that the hardness of a hardening body falls. Moreover, by setting it as 80 mass% or less, the coupling | bonding point with the functional group contained in resin does not increase too much, As a result, it can prevent that a hardening body becomes weak and a crack generate | occur | produces.
The surface modification amount of the surface modification material having one or more functional groups selected from an alkenyl group, H-Si group, and alkoxy group is more preferably 3% by mass or more and 70% by mass or less with respect to the mass of the fine particles. More preferably, it is 5 mass% or more and 60 mass% or less.

  The resin used in the encapsulating composition has substantially no light absorption in the wavelength region of light emitted from the optical semiconductor light emitting device, and the reliability (various required performance and durability) of the optical semiconductor light emitting device is achieved. It is not particularly limited as long as it is a transparent resin that is not damaged, and a transparent silicone resin, epoxy resin, acrylic resin, etc. can be used, but when assuming application to high output and lighting applications of an optical semiconductor light emitting element, It is preferable to use a general optical semiconductor light-emitting element sealing resin, and it is particularly preferable to use a silicone-based sealing resin from the viewpoint of durability. Examples of the silicone-based sealing resin include dimethyl silicone resin, methylphenyl silicone resin, diphenyl silicone resin, organically modified silicone resin, and the like, and these are cured by addition type reaction, condensation type reaction, and radical polymerization reaction.

In addition, as a method for surface modification of the fine particles, for example, a dry method in which the surface modifying material is directly mixed and sprayed on the fine particles, or the fine particles are introduced into water or an organic solvent in which the surface modifying material is dissolved, A wet method for surface modification may be mentioned.
Examples of a method for uniformly dispersing the surface-modified fine particles in the resin include, for example, a method in which the surface-modified particles and the resin are mixed and dispersed by a mechanical method such as a biaxial kneader, or the surface-modified particles are organically dispersed. There is a method of drying and removing an organic solvent after mixing a dispersion liquid dispersed in a solvent and a resin.

  The optical semiconductor light emitting device according to the present invention is manufactured by applying or injecting the sealing composition obtained as described above onto an optical semiconductor light emitting element and then curing.

[Color rendering control method]
The present invention also provides a color rendering property control method for an optical semiconductor light emitting device, in which the color rendering property is controlled by adjusting the refractive index and Abbe number of the optical semiconductor sealing material by changing the content of the fine particles.
Since the refractive index and Abbe number of the sealing material can be adjusted by the content of the fine particles, the color rendering properties of the optical semiconductor light emitting device can be controlled by adjusting the amount of light extracted from the optical semiconductor light emitting elements having different emission wavelengths. it can.
Accordingly, by controlling the color rendering properties by the above color rendering property control method, an optical semiconductor light emitting device having a good balance between the emission wavelengths of the short wavelength and the long wavelength of the light of the optical semiconductor light emitting device and having excellent color rendering properties is provided. Can do.

[Lighting fixtures and display devices]
The optical semiconductor-equipped light emitting device of the present invention can be used in various applications by taking advantage of its excellent characteristics. The effects of the present invention are particularly noticeable in various lighting fixtures and display devices having the same.

Examples of the lighting fixture include general lighting devices such as an indoor lamp and an outdoor lamp. In addition, the present invention can also be applied to lighting of a switch unit of an electronic device such as a mobile phone or OA device. Since the light-semiconductor-equipped light emitting device of the present invention is high in luminance and particularly excellent in color rendering, when used as a lighting fixture, the object to be illuminated exhibits the same color as natural light and should be used as a lighting that does not feel uncomfortable. Can do.
As a display device, for example, a mobile phone, a portable information terminal, an electronic dictionary, a digital camera, a computer, a thin TV, a lighting device, and peripheral devices thereof are reduced in size, reduced in weight, reduced in thickness, reduced in power consumption, and Examples thereof include a light-emitting device in a display device of a device that is particularly required to have high luminance and good color rendering such that good visibility can be obtained even in sunlight.

In the following Examples and Comparative Examples, various measurement methods and evaluation methods are as follows.
(Average primary particle size of fine particles)
The average primary particle diameter of the fine particles was the Scherrer diameter obtained by X-ray diffraction.

(Abbe number of fine particles)
By adjusting the pH of the water to control the dispersibility of the fine particles, an aqueous dispersion of 10% by mass of fine particles was prepared (for silica, Snowtex OS (trade name) manufactured by Nissan Chemical Industries, Ltd., 10 masses of fine particles). % Water was added). Methanol, propylene glycol monomethyl ether, and N-methylpyrrolidone were added to the aqueous dispersion to obtain a dispersion of 5% by mass of fine particles, and then the dispersion was applied onto a silicon wafer by a spin coater and dried. With respect to the silicon wafer on which the fine particle-containing coating film is formed, the refractive index at wavelengths of 407 nm, 594 nm, 632 nm, and 1523 nm is measured with a spectroscopic ellipsometer (manufactured by JA Woollam, VASE), and interpolation approximation is performed. The refractive indices n _d , n _F , and n _C of the d-line (587 nm), F-line (486 nm), and C-line (656 nm) of the Fraunhofer line are obtained, and from these values, the Abbe number ν _{d of the} sealing material is obtained. It was determined by [nu _d = formula _{(n d -1) / (n} F -n C).

(Viscosity of sealing composition)
The viscosity of the sealing composition was measured using a rheometer, Rheostress RS-6000 (manufactured by HAAKE). The viscosity of the sealing composition was measured at a temperature of 25 ° C. and a shear rate = 1.0 (1 / s).

(Transmission rate of sealing material)
After pouring the sealing composition in an amount of 0.5 mm after curing into a glass petri dish, heat treatment was performed at 100 ° C. for 2 hours and then at 150 ° C. for 4 hours to obtain a sealing material. . The transmittance from a wavelength of 400 nm to 800 nm was measured using an integrating sphere with a spectrophotometer (V-570, manufactured by JASCO Corporation) together with a glass petri dish. In addition, the transmittance | permeability of only a glass petri dish was also measured as a blank measurement. Since the transmittance at a wavelength of 400 nm is the lowest in the measurement wavelength range, the table shows the transmittance at a wavelength of 400 nm.

(Abbe number of sealing material)
With respect to the sealing material obtained in the same manner as the method for measuring the transmittance of the sealing material, the refractive index at wavelengths of 407 nm, 594 nm, 632 nm, and 1523 nm was measured with a prism coupler (2010 / M, manufactured by Metricon). The refractive index n _d , n _F , n _C of d-line (587 nm), F-line (486 nm), and C-line (656 nm) of the Fraunhofer line is obtained by interpolation approximation, and the sealing material is obtained from these values. The Abbe number ν _d was determined by the formula ν _d = (n _d −1) / (n _F −n _C ).

(Evaluation of light emission on the short wavelength side of optical semiconductor light emitting devices)
In an optical semiconductor package in which a blue light semiconductor light emitting element (InGaN type, refractive index 2.4, emission wavelength 450 nm) and a green light semiconductor element (InGaN type, refractive index 2.4, emission wavelength 530 nm) are mounted independently, The sealing compositions in Examples and Comparative Examples were injected so that the air interface shape was convex, and were cured by heat treatment at 100 ° C. for 2 hours and then at 150 ° C. for 4 hours to obtain blue and green monochromatic light. A semiconductor light emitting device (A) was produced.
Next, the refractive index in wavelength 630nm (red) was measured with the prism coupler about the sealing material which hardened the sealing composition of each Example and the comparative example.
Next, the addition amount of the fine particles is adjusted so that the refractive index at the wavelengths of 450 nm and 530 nm after curing is the refractive index of the sealing material obtained by curing the sealing compositions of the respective examples and comparative examples at a wavelength of 630 nm. In the same manner, the sealing composition prepared by adjusting the addition amount of the fine particles is projected to an optical semiconductor package in which each of the blue light semiconductor light emitting device and the green light semiconductor light emitting device is independently mounted. A monochromatic optical semiconductor light-emitting device (B) was produced by injecting and curing in a shape.
Subsequently, the brightness | luminance of each optical semiconductor light-emitting device is measured using a luminance meter (LS-110, Konica Minolta Sensing Corp.), and the optical semiconductor light-emitting device with respect to the brightness | luminance of the optical semiconductor light-emitting device (B) in each luminescent color The luminance improvement rate of (A) was calculated, and the relative extraction increase on the short wavelength side of the optical semiconductor light emitting device due to the wavelength dependency of the refractive index of the sealing material was estimated.

(Evaluation of color rendering properties of optical semiconductor light emitting devices)
Three wavelengths (colors) of a blue light semiconductor light emitting element (same as above, the same applies when not described below), a green light semiconductor light emitting element and a red light semiconductor light emitting element (AlGaInP system, refractive index 3.2, emission wavelength 630 nm) The sealing composition of each example and comparative example was injected into an optical semiconductor package having the light emitting element mounted so that the air interface shape was convex, and heat treatment was performed at 100 ° C. for 2 hours and then at 150 ° C. for 4 hours. And cured to produce a white light semiconductor light emitting device. The color rendering properties of the obtained optical semiconductor light-emitting device were measured with an LED spectrocolorimeter (Probe 4 Light, manufactured by Magantis). “X” represents a value that is smaller by 0.025 or more than the X coordinate value of 0.3 measured by the optical semiconductor package on which the light emitting element of three wavelengths (colors) whose X coordinate value is not sealed is mounted. The thing less than 0.025 was set as "(circle)".

(Evaluation of luminance of optical semiconductor light emitting device)
The sealing composition in each example and comparative example was formed into an air interface shape in an optical semiconductor package on which a light emitting element having three wavelengths (colors) of a blue light semiconductor light emitting element, a green light semiconductor light emitting element, and a red light semiconductor light emitting element was mounted. Were injected so as to have a convex shape, heated at 100 ° C. for 2 hours, and then heated at 150 ° C. for 4 hours to be cured to produce a white light semiconductor light emitting device (C).
In addition, only the resin used in the sealing compositions of the examples and comparative examples (without addition of fine particles) is formed so that the air interface shape is convex in the optical semiconductor package on which the light emitting elements of three wavelengths (colors) are mounted. Injection, heat treatment at 100 ° C. for 2 hours, and then at 150 ° C. for 4 hours and curing were carried out to produce a white light semiconductor light emitting device (D).
The luminance of each optical semiconductor light emitting device is measured using a luminance meter (LS-110, manufactured by Konica Minolta Sensing), and the luminance of the white light semiconductor light emitting device (C) is higher than the luminance of the white light semiconductor light emitting device (D). The ones with high values were “◯”, the equivalent values were “△”, and the ones with low values were “x”.

[Example 1]
(Preparation of zirconia particles)
To a zirconium salt solution in which 2615 g of zirconium oxychloride octahydrate is dissolved in 40 L (liter) of pure water, dilute ammonia water in which 344 g of 28% ammonia water is dissolved in 20 L of pure water is added with stirring, and the zirconia precursor slurry is added. Prepared.
Next, an aqueous sodium sulfate solution in which 300 g of sodium sulfate was dissolved in 5 L of pure water was added to this slurry with stirring. The amount of sodium sulfate added at this time was 30% by mass with respect to the zirconia-converted value of zirconium ions in the zirconium salt solution.
Subsequently, this mixture was dried at 130 ° C. for 24 hours in the air using a drier to obtain a solid.
Next, the solid was pulverized in an automatic mortar and then baked at 520 ° C. for 1 hour in the air using an electric furnace.
Next, the fired product is put into pure water, stirred to form a slurry, washed using a centrifuge, and after sufficiently removing the added sodium sulfate, dried in a dryer, Zirconia particles having an average primary particle size of 5.5 nm were obtained.

(Preparation of surface-modified zirconia dispersion)
Next, 82 g of toluene and 4 g of methoxy group-containing methylphenyl silicone resin (manufactured by Shin-Etsu Industrial Chemical Co., Ltd., KR9218) are added to 10 g of zirconia particles, mixed, and subjected to surface modification treatment for 5 hours with a bead mill, and then the beads are removed. did. Next, 4 g of vinyltrimethoxysilane (KBE1003, manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a vinyl group-containing modifying material, and modification / dispersion treatment was performed under reflux at 130 ° C. for 6 hours to prepare a zirconia transparent dispersion.
The surface modification amount by the alkenyl group (vinyl group) -containing surface modification material was 40% by mass with respect to the mass of the zirconia particles.

(Preparation of fine particle-containing sealing composition)
After adding 7.67 g of the trade name: ASP-1111 (manufactured by Shin-Etsu Chemical Co., Ltd.) as a diphenyl silicone resin, 50 g of the above zirconia transparent dispersion was added and stirred, and then toluene was removed by drying under reduced pressure to obtain surface-modified zirconia particles and diphenyl silicone. A fine particle-containing sealing composition containing resin (zirconia particle content: 30% by mass) was obtained.
According to the above method, the viscosity of the sealing composition, the transmittance of the sealing material and the Abbe number are measured, and the light emission amount, color rendering property and luminance on the short wavelength side of the optical semiconductor light emitting device are evaluated. Indicated.
In addition, the refractive index at each wavelength of the cured body of the fine particle-containing sealing composition was as shown in Table A below.

[Example 2]
In the production of the fine particle-containing encapsulant composition, the fine particle-containing encapsulant composition and fine particles were obtained in the same manner as in Example 1 except that the trade name: OE-6630 (manufactured by Toray Dow Corning) was used as the methylphenyl silicone resin. An optical semiconductor light emitting device including the encapsulating material is prepared, and the viscosity of the encapsulating composition, the transmittance of the encapsulating material, and the Abbe number are measured by the above-described method, and light emission on the short wavelength side of the optical semiconductor light emitting device The amount, color rendering properties and luminance were evaluated, and the results are shown in Table 1.
Moreover, the refractive index in each wavelength of the hardening body of the fine particle containing sealing composition of Example 2 was as having shown in Table B below.

[Example 3]
To 10 g of zirconia particles produced in the same manner as in Example 1, 81 g of toluene and 5 g of one-end epoxy-modified silicone (Shin-Etsu Chemical Co., Ltd., X-22-173DX) are added, mixed, and subjected to surface modification treatment with a bead mill for 5 hours. After that, the beads were removed. Next, 4 g of methyldichlorosilane (manufactured by Shin-Etsu Chemical Co., Ltd., LS-50) is added as an H—Si group-containing modifying material, and the surface is modified and dispersed at 130 ° C. under reflux for 6 hours to obtain a surface-modified zirconia transparent dispersion. A liquid was prepared.
The surface modification amount by the H—Si group-containing surface modification material was 40% by mass with respect to the mass of the zirconia particles.
Next, in the production of the fine particle-containing sealing material composition, the fine particle-containing sealing composition and the fine particle-containing composition were used in the same manner as in Example 1 using OE-6336 (manufactured by Toray Dow Corning) as the dimethyl silicone resin. An optical semiconductor light emitting device provided with a sealing material is prepared, and the viscosity of the sealing composition, the transmittance of the sealing material and the Abbe number are measured by the above-described method, and the light emission amount on the short wavelength side of the optical semiconductor light emitting device The color rendering properties and luminance were evaluated, and the results are shown in Table 1.
Moreover, the refractive index in each wavelength of the hardening body of the fine particle containing sealing composition of Example 3 was as having shown in Table C below.

[Example 4]
(Production of alumina particles)
Aluminum isopropoxide (500 g) was dissolved in 10 L of isopropanol, and 250 g of pure water was added dropwise over 4 hours, followed by heating and boiling for 15 hours. Next, an aqueous sodium sulfate solution in which 80 g of sodium sulfate was dissolved in 1.5 L of pure water was added at room temperature with stirring to obtain a mixture. This mixture was filtered and dried using a dryer at 130 ° C. for 24 hours in the air to obtain a solid. The solid was pulverized in an automatic mortar and then baked at 500 ° C. for 3 hours in the air using an electric furnace.
Next, the fired product is put into pure water, stirred to form a slurry, washed using a centrifuge, and after sufficiently removing the added sodium sulfate, dried in a dryer, Alumina particles having an average primary particle size of 8.0 nm were obtained.

(Preparation of surface-modified alumina dispersion)
Next, 81 g of toluene and 2 g of one-end epoxy-modified silicone (X-22-173DX, manufactured by Shin-Etsu Chemical Co., Ltd.) are added to 10 g of alumina particles, mixed, and subjected to surface modification treatment with a bead mill for 5 hours, and then the beads are removed. did. Next, 2.5 g of vinyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM1003) is added as a vinyl group-containing modifying material, and modification / dispersion treatment is performed under reflux at 130 ° C. for 6 hours. Surface-modified alumina transparent dispersion Was prepared.
The amount of surface modification with the alkenyl group (vinyl group) -containing surface modification material was 25% by mass with respect to the mass of the alumina particles.
Next, 2.55 g of a trade name: OE-6336 (manufactured by Toray Dow Corning Co., Ltd.) as a dimethyl silicone resin was added to 14.5 g of the above surface-modified alumina transparent dispersion, stirred, and then encapsulated with fine particles in the same manner as in Example 1. An optical semiconductor light emitting device provided with a fine particle-containing encapsulant was obtained by obtaining a stop composition (alumina particle content: 25% by mass), and the viscosity of the encapsulant and the penetration of the encapsulant were obtained by the above-described methods. The rate and the Abbe number were measured, and the light emission amount, color rendering properties and luminance on the short wavelength side of the optical semiconductor light emitting device were evaluated. The results are shown in Table 1.
Moreover, the refractive index in each wavelength of the hardening body of the fine particle containing sealing composition of Example 4 was as having shown in Table D below.

[Example 5]
A photo-semiconductor light-emitting device provided with a fine particle-containing sealing composition in the same manner as in Example 4 except that the alumina particle content in the fine particle-containing sealing composition was 50% by mass. The viscosity of the sealing composition, the transmittance of the sealing material, and the Abbe number are measured by the above-described method, and the light emission amount, color rendering property, and luminance on the short wavelength side of the optical semiconductor light emitting device are evaluated. Are shown in Table 1.
Moreover, the refractive index in each wavelength of the hardening body of the fine particle containing sealing composition of Example 5 was as having shown in Table E below.

[Example 6]
82 g of toluene and 2 g of methoxy group-containing methylphenylsilicone resin (manufactured by Shin-Etsu Kogyo Kagaku Co., Ltd., KR9218) are added to 10 g of alumina particles produced in the same manner as in Example 4, mixed, and subjected to surface modification treatment with a bead mill for 5 hours. After that, the beads were removed. Next, 2.5 g of vinyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM1003) is added as a vinyl group-containing modifying material, and modification / dispersion treatment is performed under reflux at 130 ° C. for 6 hours. Surface-modified alumina transparent dispersion Was prepared.
The amount of surface modification with the alkenyl group (vinyl group) -containing surface modification material was 25% by mass with respect to the mass of the alumina particles.
Next, 2.75 g of a trade name: OE-6630 (manufactured by Toray Dow Corning Co., Ltd.) as a methylphenyl silicone resin was added to 50 g of the surface-modified alumina transparent dispersion, stirred, and then encapsulated with fine particles in the same manner as in Example 1. A composition (alumina particle content: 50% by mass) was obtained, and an optical semiconductor light-emitting device equipped with a fine particle-containing encapsulant was produced. By the above-described methods, the viscosity of the encapsulant and the transmittance of the encapsulant were obtained. The Abbe number was measured, and the light emission amount, color rendering properties and luminance on the short wavelength side of the optical semiconductor light emitting device were evaluated. The results are shown in Table 1.
Moreover, the refractive index in each wavelength of the hardening body of the fine particle containing sealing composition of Example 6 was as having shown in Table F below.

[Example 7]
(Preparation of surface-modified silica dispersion)
50 g of a methanol solution in which 2.5 g of hexanoic acid was dissolved in 100 g of silica sol (manufactured by Nissan Chemical Industries, Ltd., Snowtex OS) was mixed and stirred, and the solvent was dried and removed with an evaporator. When the Scherrer diameter of the silica particles of the obtained silica particle-containing dry powder was measured by X-ray diffraction, the average primary particle diameter was 9.5 nm. Furthermore, 12.5 g of the silica particle-containing dry powder was mixed with 86.5 g of toluene. Next, 2 g of methoxy group-containing methylphenyl silicone resin (manufactured by Shin-Etsu Chemical Co., Ltd., KR9218) is added, modified and dispersed under reflux at 130 ° C. for 6 hours, the dispersion is passed through an alumina column, and hexanoic acid is added. Removed. Furthermore, 1.5 g of vinyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM1003) was added and subjected to modification / dispersion treatment under reflux at 130 ° C. for 6 hours to prepare a surface-modified silica transparent dispersion.
The amount of surface modification by the alkenyl group (vinyl group) -containing surface modification material was 15% by mass with respect to the mass of the silica particles.
After adding 9.95 g of a trade name: OE-6630 (manufactured by Dow Corning Toray) as a methylphenyl silicone resin to 50 g of the above silica transparent dispersion, toluene is removed by drying under reduced pressure, and surface-modified zirconia particles and diphenyl are added. Obtaining a fine particle-containing encapsulating composition (silica particle content: 30% by mass) containing a silicone resin, producing an optical semiconductor light-emitting device equipped with a fine particle-containing encapsulant, and sealing composition according to the above method The viscosity of the product, the transmittance of the sealing material, and the Abbe number were measured, and the light emission amount, color rendering properties, and luminance on the short wavelength side of the optical semiconductor light emitting device were evaluated. The results are shown in Table 1.
Moreover, the refractive index in each wavelength of the hardening body of the fine particle containing sealing composition of Example 7 was as having shown in Table G below.

[Comparative Example 1]
(Production of titania particles)
242.1 g of titanium tetrachloride and 111.9 g of tin (IV) chloride pentahydrate were put into 1.5 L (liter) of pure water at 5 ° C. and stirred to prepare a mixed solution.
Next, the mixed solution is heated to adjust the temperature to 25 ° C., and an aqueous ammonium carbonate solution having a concentration of 10% by mass is added to the mixed solution to adjust the pH to 1.8, and then 24 ° C. at 24 ° C. Aged for time to remove excess chloride ions.
Subsequently, moisture was removed from this mixed solution using an evaporator, and then dried to produce titanium oxide particles.
The average primary particle diameter of the obtained titanium oxide particles was 5.0 nm.
A surface-modified titania transparent dispersion was obtained in the same manner as in Example 1 except that the titania particles were used.
The surface modification amount by the alkenyl group (vinyl group) -containing surface modification material was 40% by mass with respect to the mass of the titania particles.
Further, a titania fine particle-containing diphenyl silicone sealing composition (titania particle content: 30% by mass) was obtained in the same manner as in Example 1 except that the above titania transparent dispersion was used, and provided with a fine particle-containing sealing material. An optical semiconductor light-emitting device is manufactured, and the viscosity of the sealing composition, the transmittance of the sealing material, and the Abbe number are measured by the above-described method, and the light emission amount, color rendering property, and luminance on the short wavelength side of the optical semiconductor light-emitting device are measured. The results are shown in Table 1.
Moreover, the refractive index in each wavelength of the hardening body of the fine particle containing sealing composition of the comparative example 1 was as having shown in Table H below.

[Comparative Example 2]
To 10 g of titania particles produced in the same manner as in Comparative Example 1, 81 g of toluene and 5 g of one-end epoxy-modified silicone (manufactured by Shin-Etsu Chemical Co., Ltd., X-22-173DX) are added, mixed, and subjected to surface modification treatment with a bead mill for 5 hours. After doing so, the beads were removed. Next, 4 g of vinyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM1003) is added as a vinyl group-containing modifying material, and modification / dispersion treatment is performed under reflux at 130 ° C. for 6 hours to prepare a surface-modified titania transparent dispersion. did.
The surface modification amount by the alkenyl group (vinyl group) -containing surface modification material was 40% by mass with respect to the mass of the titania particles.
Subsequently, 20 g of the above-mentioned titania transparent dispersion and 6.2 g of a trade name: OE-6336 (manufactured by Toray Dow Corning) as a dimethyl silicone resin were added, stirred, and used in the same manner as in Example 1 to contain a fine particle-containing sealing composition. (Titania particle content: 20% by mass), an optical semiconductor light emitting device provided with a fine particle-containing encapsulant is prepared, and the viscosity of the encapsulating composition, the transmittance of the encapsulant, and the Abbe number are measured by the above-described methods. Then, the light emission amount, color rendering properties and luminance on the short wavelength side of the optical semiconductor light emitting device were evaluated, and the results are shown in Table 1.
Moreover, the refractive index in each wavelength of the hardening body of the fine particle containing sealing composition of the comparative example 2 was as having shown in Table I below.

[Comparative Example 3]
The zirconia of Comparative Example 3 was the same as Example 1 except that the alkenyl group-containing modified material of Example 1 was changed to an alkyl group-containing surface modified material using hexyltrimethoxysilane (KBE3063, manufactured by Shin-Etsu Chemical Co., Ltd.). A fine particle-containing diphenyl silicone sealing composition was prepared, and an optical semiconductor light emitting device provided with the fine particle-containing sealing material was prepared.
However, the fine particle-containing sealing composition of Comparative Example 3 became cloudy during the heat curing process and did not become a transparent cured product. Therefore, the Abbe number of the sealing material, the light emission amount on the short wavelength side of the optical semiconductor light emitting device, and the color rendering properties could not be evaluated. Table 1 shows the evaluation results of the viscosity of the sealing composition, the transmittance of the sealing material, and the luminance of the optical semiconductor light emitting device.

[Comparative Example 4]
Zirconia particles having an average primary particle size of 1.9 nm were prepared in the same manner as in Example 1 except that 520 ° C. was changed to 490 ° C. in the atmosphere using an electric furnace.
Further, in the same manner as in Example 1, a zirconia fine particle-containing diphenyl silicone sealing composition of Comparative Example 4 was produced.
However, the fine particle-containing encapsulating composition of Comparative Example 4 has a very high viscosity, cannot produce a cured body capable of measuring the refractive index, and cannot be injected into a package equipped with an optical semiconductor light emitting device. A semiconductor light emitting device could not be fabricated. Therefore, the Abbe number of the sealing material, the light emission amount on the short wavelength side of the optical semiconductor light emitting device, the color rendering property and the luminance could not be evaluated. The evaluation results of the viscosity of the sealing composition and the transmittance of the sealing material are shown in Table 1.

[Comparative Example 5]
Zirconia particles having an average primary particle size of 21.1 nm were prepared in the same manner as in Example 1 except that 520 ° C. was changed to 620 ° C. in the atmosphere using an electric furnace.
To 10 g of zirconia particles, 82 g of toluene and 1 g of methoxy group-containing methylphenyl silicone resin (manufactured by Shin-Etsu Kogyo Kagaku Co., Ltd., KR9218) were added, mixed, subjected to surface modification treatment for 5 hours with a bead mill, and then the beads were removed. Next, 1 g of vinyltrimethoxysilane (KBE1003, manufactured by Shin-Etsu Chemical Co., Ltd.) was added as a vinyl group-containing modifying material, and modification / dispersion treatment was performed under reflux at 130 ° C. for 6 hours to prepare a zirconia transparent dispersion.
The surface modification amount by the alkenyl group-containing surface modifying material was 10% by mass with respect to the mass of the zirconia particles.
Next, 50 g of the above zirconia transparent dispersion was added as a diphenyl silicone resin with 10.67 g of trade name: ASP-1111 (manufactured by Shin-Etsu Chemical Co., Ltd.), stirred, and then toluene was removed by drying under reduced pressure to obtain surface-modified zirconia particles and A fine particle-containing encapsulating composition (zirconia particle content: 30% by mass) containing diphenyl silicone resin was produced, and an optical semiconductor light-emitting device provided with the fine particle-containing encapsulant was produced.
However, the fine particle-containing sealing composition of Comparative Example 5 was milky white and did not become a transparent sealing composition or a cured product. Therefore, the Abbe number of the sealing material, the light emission amount on the short wavelength side of the optical semiconductor light emitting device, and the color rendering properties could not be evaluated. Table 1 shows the evaluation results of the viscosity of the sealing composition, the transmittance of the sealing material, and the luminance of the optical semiconductor light emitting device.

10, optical semiconductor light emitting element 11, phosphor 12, optical semiconductor sealing material layer 13, air interface 14, resin single layer

Claims (6)

An optical semiconductor light emitting device comprising two or more optical semiconductor light emitting elements having different emission wavelengths,
The sealing composition containing the fine particles and the resin is cured, the Abbe number of the optical semiconductor light emitting element is sealed by the optical semiconductor encapsulation is 30 or more,
The sealing composition, the fine particles are zirconium oxide or aluminum oxide, fine particles, an alkenyl group, by surface modification material having one or more functional groups selected from H-Si group and an alkoxy group, surface-modified, Ri Do from free material absorption of light in the optical semiconductor light-emitting wavelength region, an average primary particle diameter of 3nm or more, Ri Ah at 20nm or less fine particles,
The optical semiconductor light emitting device , wherein the resin is a dimethyl silicone resin or a silicone resin having a phenyl group . 2. The optical semiconductor light emitting device according to claim 1, wherein a transmittance from a wavelength of 400 nm to a wavelength of 800 nm of the optical semiconductor sealing material is 70% or more. Controlling the color rendering properties by adjusting the refractive index of the optical semiconductor sealing material and the Abbe number by Rukoto adjusting the type and content of the resin and the fine particles, an optical semiconductor light emitting device according to claim 1 or 2 Color rendering control method. An optical semiconductor light emitting device in which color rendering is controlled by the color rendering control method according to claim 3 . The lighting fixture which comprises the optical semiconductor light-emitting device in any one of Claims 1-2 and 4 . Display device comprising comprising an optical semiconductor light-emitting device according to any one of claims 1 to 2 and 4.